JP2750399B2 - Heat resistant photosensitive resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition, and more particularly, to a solder resist (solder register), an etching resist and a plating resist used for manufacturing a printed wiring board. The present invention relates to a heat-resistant photosensitive resin composition having excellent heat resistance and adhesion as well as high sensitivity.

[Conventional technology]

Conventionally, it is well known that a photosensitive resin is used as a solder resist, an etching resist and a plating resist in the manufacture of a printed wiring board.

For example, Japanese Unexamined Patent Publication (Kokai) No. 60-208377 discloses a solder comprising a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a photopolymerization initiator and an amine type curing agent provided with a group having an ethylenically unsaturated double bond. A resist is disclosed. JP-A-58-199341
Japanese Patent Application Publication No. JP-A-2003-115139 discloses a heat-resistant photosensitive resin composition containing a diallyl phthalate prepolymer, a photopolymerizable monomer and a photopolymerization initiator. JP-A-52-43090 discloses a photopolymerizable resin containing a linear polymer compound having an N-alkoxymethylcarbamoyl group in a side chain and a compound having at least two epoxy groups. .

[Problems to be solved by the invention]

Such a heat-resistant photosensitive resin composition has a characteristic that it is excellent in heat resistance and chemical resistance, but has a drawback that it can be developed only with a specific organic solvent such as a chlorine-based organic solvent. Therefore, an expensive organic solvent must be used for the development process, which is economically disadvantageous.

Also, from the viewpoints of pollution prevention and environmental hygiene, the use of chlorinated organic solvents has tended to be avoided, and the organic solvents usable for development have been increasingly limited.

In order to solve such a problem, a water-resistant or alkali-developed heat-resistant photosensitive resin has been developed.
Insufficient chemical resistance, heat resistance, adhesion, storage stability,
Nothing was practical.

[Means for solving the problem]

As a result of intensive research to solve such problems,
Combining alkali-soluble and thermosetting specific copolymers with photopolymerizable and thermopolymerizable epoxidized triazines allows for an alkaline aqueous solution with excellent heat resistance, adhesion, chemical resistance, and electrical insulation. They have found that a photosensitive resin composition that can be developed is obtained, and have completed the present invention.

That is, the present invention provides: a) a copolymer represented by the general formula: (Where X is a hydrogen atom or a methyl group, and Y is a carbon atom 1
, An alkylene group having 1 to 4 carbon atoms, Z is an alkyl group having 1 to 4 carbon atoms or a benzyl group), and 10 to 30% by weight of an ethylenically unsaturated compound having a carboxyl group and 10 to 30% by weight. A polymer b, an epoxidized triazine c, a photopolymerizable monomer d, a photopolymerization initiator e, and a solid powder obtained by blending 40 to 80% by weight of a polymerizable ethylenically unsaturated compound and copolymerizing the same. It is a heat-resistant photosensitive resin composition as an essential component.

The copolymer used in the present invention has a general formula as a copolymer component. (Where X is a hydrogen atom or a methyl group, and Y is a carbon atom 1
To 4 alkylene groups and Z is an alkyl group having 1 to 4 carbon atoms or a benzyl group). Such compounds include N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-propoxymethylacrylamide,
Propoxymethyl methacrylamide, Nn-butoxymethylacrylamide, Nn-butoxymethylmethacrylamide, N-iso-butoxymethylacrylamide, N-iso-butoxymethylmethacrylamide, N-
Examples include benzyloxymethyl acrylamide, Nn-butoxyethyl acrylamide, Nn-butoxyethyl methacrylamide, N-iso-butoxyethyl acrylamide, N-iso-butoxyethyl methacrylamide, and the like.

These are used alone or in combination of two or more, and are used in an amount of 10 to 30% by polymerization based on the total amount of the copolymer components. If the compounding ratio is larger than this range, development with an alkaline aqueous solution becomes difficult, which is not practical. If the amount is small, sufficient heat resistance cannot be obtained.

Further, the copolymer used in the present invention must contain an ethylenically unsaturated compound having a carboxyl group as a copolymer component. Representative examples of such compounds include acrylic acid and methacrylic acid, but are not limited thereto.

These are used alone or in combination of two or more, and are used in an amount of 10 to 30% by weight based on the total amount of the copolymer components. If the amount is less than this range, the developability deteriorates and no pattern is formed. Further, a photosensitive composition using a copolymer having a larger amount than this range is not preferred because storage stability is deteriorated and gelation is liable to occur, and furthermore, electric insulation is deteriorated.
Further, an ethylenically unsaturated compound having a carboxyl group is used as one of the copolymerization components, and the acid value of the copolymer is 5 to 5.
By being in the range of 300, preferably 100-200,
The heat-resistant photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution.

Furthermore, in the copolymer of the present invention, an ethylenically unsaturated compound copolymerizable with the above-mentioned copolymer component other than the above-mentioned copolymer component is used in an amount of 40 to 80% by weight based on the total amount of the copolymer component. As these copolymerizable ethylenically unsaturated compounds, styrene, α-methylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxymethyl acrylate,
Examples include, but are not limited to, hydroxymethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate. When the amount of the copolymerizable ethylenically unsaturated compound is larger than the above range, development with an alkaline aqueous solution becomes difficult, and heat resistance is lowered, so that it is not practical. If the amount is less than the above range, the storage stability is deteriorated, which is not preferable.

The copolymer in the present invention has a function of improving the heat resistance of the obtained pattern by self-crosslinking by heat treatment after pattern formation by exposure and development treatment.

Epoxidized triazine (hereinafter referred to as TE) used in the present invention.
PIC) is a trivalent epoxy compound having a triazine nucleus as a skeleton, that is, tri- (2,3-epoxypropyl).
Isocyanurate, white granules or powder. Because TEPIC has an epoxy group in the molecule, when an image patterned using the heat-resistant photosensitive resin composition of the present invention is heated, the image is converted to heat-resistant by the reaction with the carboxyl group in the composition. can do.

The photosensitive resin composition of the present invention includes the above copolymer, TEPI
A photopolymerizable monomer is required in addition to C. Such monomers include methyl acrylate, methyl methacrylate, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate,
Trimethylolpropane dimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetrimethacrylate, tetramethylolpropanetetraacrylate, tetramethylolpropanetetramethacrylate, pentaerythritol triacrylate,
Pentaerythritol trimethacrylate, dipentaerythritol petaacrylate, dipentaerythritol pentamethacrylate, 1,1,1-tri (acryloxypropoxypropoxymethyl) propane (C ₂ H ₅ C [CH ₂ O
(C ₃ H ₆ O) ₂ COCH = CH ₂ ] ₃ ), melamine acrylate obtained by reacting 1 mol of hexamethomethoxymethyl melamine with 1 mol or more of hydroxyalkyl acrylate or hydroxyalkyl methacrylate, epoxy of phenol novolak type epoxy resin It is a carboxy group-containing esterified resin obtained by reacting an acid anhydride of a divalent carboxylic acid with a hydroxyl group generated by reacting a group with acrylic acid or methacrylic acid, but is not limited thereto.

Of these, melamine acrylate obtained by reacting hexamethoxymethyl melamine with hydroxyalkyl acrylate or hydroxyalkyl methacrylate can be made into 1 to 6 acrylates by adjusting the reaction molar ratio, and these can be used as needed. Can be selected appropriately.

Such melamine acrylate, after converting melamine to hexamethoxymethyl melamine via hexamethylol melamine, is reacted with hydroxyalkyl acrylate or hydroxyalkyl methacrylate such as hydroxytetyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate. Can be obtained by Such a melamine acrylate reacts with the copolymer by heating and cures when a methoxy group remains in the melamine acrylate molecule even after being photopolymerized by ultraviolet irradiation, thereby further improving the heat resistance. There is.

The mixing ratio of the copolymer and the photopolymerizable monomer in the photosensitive resin composition of the present invention, when the copolymer is 100 parts by weight, TEPIC is 20 to 80 parts by weight, the photopolymerizable monomer is. Desirably, it is 25 to 250 parts by weight.

A conventionally known photopolymerization initiator in the present invention can be used. For example, benzophenone,
Benzophenones such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone,
Ethyl anthraquinone, anthraquinones such as tert-butylanthraquinone, benzoin ethyl ethers, benzoin alkyl ethers such as benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-chlorothioxanthone, Diethylthioxanthone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-1-propanone and the like, and one or more of these are 0.1 to 20% by weight based on the components including the copolymer, TEPIC and the photopolymerizable monomer.
%.

Aerosil (Si
O ₂ ), mica, talc, aluminum oxide (Al ₂ O ₃ ),
Inorganic solid powders such as aluminum hydroxide and antimony oxide, and organic solid powders such as spherical benzoguanidine resin, granular polyimide, and granular polyamide can be used. The blending ratio of the solid powder can be appropriately adjusted depending on the type and purpose of the powder, but as a rough guide, it is blended in the photosensitive resin composition of the present invention in an amount of 1 to 70% by weight.

Further, in the present invention, an epoxy curing agent can be compounded and used as needed, and such an epoxy curing agent is generally known as an amine curing agent, an acid anhydride curing agent, a phenol resin, a melamine resin, Although a cationic epoxy curing agent can be used, in the present invention, it is particularly preferable to use an amine curing agent and a cationic epoxy curing agent because they have little effect on sensitivity. Examples of such epoxy curing agents include 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl4,5-dihydroxysimethylimidazole, and isocyanuric acid adduct of 2-methylimidazole ( Imidazoles such as 2MZ-OK manufactured by Shikoku Chemicals, and 1- (4,5-diamino-2-triazinyl) -2- (2-methyl-1-imidazoline) ethane (2MZ-AZINE manufactured by Shikoku Chemicals) Compounds, tertiary amines such as benzylmethylamine and dimethylaminomethylphenol, amino complex compounds such as boron trifluoride monoethylamine, and boron trifluoride triethanolamine, and cationic epoxy curing that generates Lewis acids upon irradiation with ultraviolet light Agents (CG-24-61 manufactured by Ciba-Geigy) and the like are effective.

The amount of these epoxy curing agents used is 1 per TEPIC.
It is in the range of -20% by weight, preferably 2-10% by weight. If the amount of the epoxy curing agent is less than 1% by weight, it takes a long time for heat curing, and the effect as an epoxy curing agent is not exhibited. If it is more than 20% by weight, the stability will be poor.

In addition, silicone or fluorine defoamers, hydroquinone to prevent gelation and improve storage stability,
Polymerization inhibitors such as methylhydroquinone and hydroquinone monomethyl ether, and coloring agents such as dyes and pigments can be added.

Examples of the solvent for dissolving the heat-resistant photosensitive resin of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. Ether solvents and their acetate solvents, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are preferred. In addition, a petroleum-based solvent can be used as a diluent for the purpose of adjusting the viscosity. Examples of such a petroleum-based solvent include swazole (manufactured by Maruzen Petroleum) and Solvesso (manufactured by Tonen Petrochemical).

 Next, examples of use of the present invention will be described.

When the heat-resistant resin composition of the present invention is used as a solder resist, it has a through hole and is coated with a roll coater, a curtain flow coater, an electrostatic coating or the like on both sides of a printed wiring board on which a circuit is formed, and dried. Later
Ultraviolet rays are irradiated through a negative mask, and the unexposed portion of the resin is removed with a weak alkaline aqueous solution such as sodium carbonate. Further, by performing heat curing at 100 to 200 ° C., a solder resist pattern can be formed.

When used as a plating resist, for example, both sides of a copper-clad laminate are coated with a roll coater or the like, dried, then exposed through a negative mask, and the unexposed portion of the resin is removed with a weak alkaline aqueous solution to form a pattern. To perform a plating process. At this time, the plating treatment is preferably neutral or acidic plating.

Similarly, when used as an etching resist, after a pattern is formed on a copper-clad laminate, copper is etched with an aqueous ferric chloride solution or the like. The resist film can be easily removed with a strong alkaline solution such as an aqueous sodium hydroxide solution.

〔Example〕

Next, the present invention will be described in more detail by way of examples. All parts and percentages are parts by weight and% by weight.

Example 1 A separable flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 40 parts of methyl methacrylate and 20 parts of styrene.
Parts, methacrylic acid 20 parts, N-iso-butoxymethylacrylamide (IBMA manufactured by Nitto Riken Kogyo Co., Ltd.) 20 parts, ethylene glycol monobutyl ether 60 parts, diethylene glycol monoethyl ether 40 parts, radical polymerization initiator (Wako Pure Chemical Industries, Ltd. 2 parts of -65,2,2'-azobis- (2,4-dimethylvaleronitrile) were added, and a polymerization reaction was carried out at 70 ° C. This gives copolymer A having an acid value of 130 and an average molecular weight of 48,000.
I got

100 parts of copolymer A TEPIC (manufactured by Nissan Chemical Industries) 40 Trimethylolpropane triacrylate 30 (A-TMPT manufactured by Shin-Nakamura Chemical Co.) diethylthioxanthone 3 (DETX manufactured by Nippon Kayaku) 2,2-dimethoxy-2- Phenylacetophenone 4 (Irgacure 651 manufactured by Ciba Geigy) Aerosil 200 (manufactured by Nippon Aerosil) 6 Silicone-based defoamer 2 (KS-603 manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and the mixture was thoroughly kneaded with a three-roll mill. To obtain a uniform resin composition. This was coated on one side of a printed wiring board having through holes by a roll coater, dried at 80 ° C. for 15 minutes, then coated on the opposite side in the same manner, and dried at 80 ° C. for 30 minutes. After confirming that the coated surface had returned to room temperature, it was irradiated with 400 mJ / cm ² ultraviolet light through a negative mask, and then the unexposed portion of the resin was removed with a 1.5% aqueous sodium carbonate solution (30 ° C.) for 100 seconds. . Further, heat curing was performed at 140 ° C. for 60 minutes to obtain a printed wiring board on which a solder resist pattern was formed.

A rosin flux of pH 2 was applied to this substrate to activate the metal terminals in the through holes, and then immersed in molten solder at 260 ° C for 1 minute, but no discoloration or blistering of the resin on the circuit was observed. Was. In order to remove the rosin-based flux, it was immersed in boiling methylene chloride for 10 minutes, but no change was observed.

Example 2 A separable flask equipped with a thermometer, a stirrer and a cooling condenser was charged with 40 parts of methyl methacrylate and 20 parts of styrene.
Parts, methacrylic acid 20 parts, Nn-butoxyethyl acrylamide 20 parts, ethylene glycol monobutyl ether
60 parts, diethylene glycol monoethyl ether 40 parts,
3 parts of a radical polymerization initiator (V-65, 2,2'-azobis- (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.) was added, and a polymerization reaction was performed at 70 ° C. Thus, a copolymer B having an acid value of 130 and an average molecular weight of 38,000 was obtained.

100 parts of copolymer B TEPIC (manufactured by Nissan Chemical Industries, Ltd.) 40 Trimethylolpropane triacrylate 30 benzophene 4,4,4-diethylaminobenzophenone 1 Aerosil @ 300 (manufactured by Nippon Aerosil Co., Ltd.) 6 and kneaded well with a three-roll mill Was performed to obtain a uniform resin composition. This is coated on one side of the printed wiring board with a through hole through a 150 mesh Tetron screen, the circuit is formed, dried at 80 ℃ for 15 minutes, and then coated on the other side in the same way And dried at 80 ° C. for 30 minutes. After cooling to room temperature, irradiated with ultraviolet rays of 500 mJ / cm ² through a negative mask, followed
Unexposed portions of the resin were removed with a 1.5% aqueous sodium carbonate solution (30 ° C.) for 100 seconds. Further, heat curing was performed at 140 ° C. for 60 minutes to obtain a printed wiring board on which a solder resist pattern was formed.

After applying a rosin-based flux of pH2 to this substrate to activate the metal terminals in the through-holes, it was immersed in molten solder at 260 ° C for 1 minute.
No blisters were seen. In addition, immersion in boiling methylene chloride for 10 minutes to remove the rosin-based flux showed no change.

Example 3 A separable flask equipped with a thermometer, a stirrer and a cooling condenser was charged with 45 parts of methyl methacrylate and 15 parts of styrene.
Part, methacrylic acid 25 parts, Nn-butoxymethylacrylamide 15 parts, ethylene glycol monobutyl ether
60 parts, diethylene glycol monoethyl ether 60 parts,
3 parts of a radical polymerization initiator (V-65, 2,2'-azobis- (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.) was added, and a polymerization reaction was performed at 70 ° C. Thus, a copolymer C having an acid value of 150 and an average molecular weight of 46,000 was obtained.

100 parts of copolymer C TEPIC (manufactured by Nissan Chemical Industries, Ltd.) 60 trimethylolpropane triacrylate 40 diethylthioxanthone 5 (manufactured by Nippon Kayaku Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 3 Aerosil♯300 (Nippon Aerosil Co., Ltd.) 6) Silicone-based antifoaming agent 2 (KS-603 manufactured by Shin-Etsu Silicone Co., Ltd.) was taken and sufficiently kneaded with a three-roll mill to obtain a uniform resin composition. This was coated on one side of a printed wiring board to which a circuit was previously wired through a 150-mesh Tetron screen and having through holes. After drying at 80 ° C. for 15 minutes, the other side was coated in the same manner and dried at 80 ° C. for 30 minutes. After cooling to room temperature, the film was irradiated with 400 mJ / cm ² ultraviolet light through a negative mask. The unexposed portion of the resin was removed with a 1.0% aqueous sodium carbonate solution (35 ° C.) for 120 seconds.
Further, heat curing was performed at 140 ° C. for 60 minutes to obtain a printed wiring board on which a solder resist pattern was formed.

After applying a rosin-based flux of pH 2 to this substrate to activate the metal terminals in the through holes, the substrate was immersed in molten solder at 260 ° C for 30 seconds, and then immersed in methylene chloride for 60 seconds. No change was observed, and a peel test using cellophane tape was performed. As a result, it was found that the adhesiveness was excellent.

Example 4 100 parts of the copolymer A of Example 1 TEPIC (manufactured by Nissan Chemical Industries, Ltd.) 60 Phenol novolak type epoxy acrylate 60 having a carboxyl group (SP-4300-IX manufactured by Showa Polymer Co., Ltd.) Trimethoxymethylmelamine trimethoxy Ethyl acrylate 30 (Nikarac MX-302 manufactured by Sanwa Chemical Co., Ltd.) Trimethylolpropane triacrylate 20 pentaerythriether tetraacrylate 20 diethylthioxanthone 3 (DETX manufactured by Nippon Kayaku Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 4 ( Irgacure 651 manufactured by Ciba Geigy) Aerosil 300 (manufactured by Nippon Aerosil) 10 Talc P-4 (manufactured by Nippon Talc) 60 1- (4,5-diamino-2-triazinyl) -2-
(2-Methyl-1-imidazolyl) ethane 3 (2MZ-AZINE manufactured by Shikoku Chemicals) 1 part of cyanine green Silicone-based defoamer 2 (KS-603 manufactured by Shin-Etsu Silicone Co., Ltd.) Kneading was performed to obtain a uniform resin composition. This was coated on one side of a printed wiring board with a through-hole through a 150-mesh Tetron screen and a circuit was formed at 80 ° C.
After drying for 15 minutes and then coating on the opposite side, it was dried at 80 ° C. for 30 minutes. After cooling to room temperature, irradiated with ultraviolet rays of 600 mJ / cm ² through a negative mask, followed
Unexposed portions of the resin were removed with a 1.0% aqueous sodium carbonate solution (30 ° C.) for 80 seconds. Further, heat curing was performed at 140 ° C. for 60 minutes to obtain a printed wiring board on which a solder resist pattern was formed.

After applying a rosin-based flux of pH2 to this board to activate the metal terminals in the through-holes, the board was immersed in molten solder at 260 ° C for 1 minute, but no discoloration or flaking of the resin on the circuit was observed. Was. In order to remove the rosin-based flux, it was immersed in boiling methylene chloride for 10 minutes, but no change was observed. Further immersion in boiling ethylene glycol monoethyl ether for 10 minutes showed no change.

Example 5 100 parts of the copolymer C of Example 3 TEPIC (manufactured by Nissan Chemical Industries, Ltd.) 50 Phenol novolak type epoxy acrylate having a carboxy group 60 (SP-4300-IX manufactured by Showa Polymer Co., Ltd.) Trimethoxymethylmelamine trimethoxy Ethyl acrylate 40 (Nikarac MX-302 manufactured by Sanwa Chemical Co., Ltd.) Trimethylolpropane pantriacrylate 30 dipentaerythritol pentaacrylate 20 diethylthioxanthone (DETX manufactured by Nippon Kayaku Co., Ltd.) 3 2,2-dimethoxy-2-phenylacetophenone 4 ( Irgacure 651 manufactured by Ciba Geigy) Aerosil 380 (manufactured by Nippon Aerosil) 10 parts Barium sulfate 50 2-phenyl-4,5-dihydroxymethylimidazole 4 (2PHZ manufactured by Shikoku Chemicals) Cyanine green 1 Silicone-based defoamer 2 (Shin-Etsu Silicone KS-603) The mixture was sufficiently kneaded with a three-roll mill to obtain a uniform resin composition. This was coated on one side of a printed wiring board having a through-hole through a 150-mesh Tetron screen, on which a circuit was formed, and heated at 80 ° C for 15 minutes.
Dried for 30 minutes, then coated on the back side
Dried for minutes. After cooling to room temperature, ultraviolet rays of 600 mJ / cm ² were irradiated through a negative mask, and the unexposed portion of the resin was removed with a 1.0% aqueous sodium carbonate solution (30 ° C.) for 80 seconds. Further, heat curing was performed at 140 ° C. for 60 minutes to obtain a printed wiring board on which a solder resist pattern was formed.

After applying a rosin-based flux of pH2 to this board to activate the metal terminals in the through-holes, the board was immersed in molten solder at 260 ° C for 1 minute, but no discoloration or flaking of the resin on the circuit was observed. Was. In order to remove the rosin-based flux, it was immersed in boiling methylene chloride for 10 minutes, but no change was observed.

Example 6 The entire surface of the copper-clad laminate was coated with the photosensitive resin composition obtained in Example 2 using a roll coater and dried at 80 ° C. for 30 minutes. After cooling to room temperature, irradiated with ultraviolet rays of 400 mJ / cm ² through a negative mask, which is formed of a pattern then 1.0% aqueous sodium carbonate solution (30 ° C.) by removing the 60 seconds over an unexposed portion of the resin resist A membrane was obtained. This substrate was subjected to electrolytic plating in a copper sulfate plating bath to give a copper plating having a thickness of 20 μm. A sharp plating pattern was formed on the resist film after plating without any plating.

Example 7 The photosensitive resin composition obtained in Example 1 was coated on a copper-clad laminate through a 150-mesh screen made of Tetron, dried at 80 ° C. for 30 minutes, cooled to room temperature, and then subjected to a negative mask. Was irradiated with ultraviolet rays at 500 mJ / cm ² . Afterwards, the solution is treated with a 1.0% aqueous sodium carbonate solution (30 ° C)
The unexposed portion of the resin was removed over a period of seconds to obtain a resist film on which a pattern was formed.

The exposed copper was then etched on the substrate with an aqueous ferric chloride solution. After completion of the etching, the resist film was removed with a 1.0% aqueous sodium hydroxide solution (40 ° C.), and a copper circuit pattern faithful to the negative mask was obtained.

Comparative Example 1 In a separable flask equipped with a thermometer, a stirrer, and a cooling condenser, 60 parts of methyl methacrylate, 20 parts of isobutyl methacrylate, 20 parts of methacrylic acid, 60 parts of ethylene glycol monobutyl ether, 40 parts of diethylene glycol monoethyl ether, Two parts of a radical polymerization initiator (V-65, 2,2'-azobis- (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.) was added, and a polymerization reaction was performed at 70 ° C. Thus, a copolymer D having an acid value of 130 and an average molecular weight of 45,000 was obtained.

100 parts of copolymer D TEPIC (manufactured by Nissan Chemical Industries) 40 Trimethylolpropane triacrylate 30 diethylthioxanthone 3 (DETX manufactured by Nippon Kayaku) 2,2-dimethoxy-2-phenylacetophenone 4 (Irgacure 651 manufactured by Ciba-Geigy) ) Aerosil No. 300 (manufactured by Nippon Aerosil Co., Ltd.) 6 2-Phenyl-4,5-dihydroxymethylimidazole 3 (manufactured by Shikoku Chemicals Co., Ltd. 2PHZ) Silicone defoamer 2 (KS-603 manufactured by Shin-Etsu Silicone Co., Ltd.) The mixture was sufficiently kneaded with this roll mill to obtain a uniform resin composition. This was coated on one side of a printed wiring board on which circuits were previously wired through a 150-mesh screen made of Tetron. This at 80 ° C for 10
Dry for another minute and coat the other side in the same way, 80
Dry at 20 ° C. for 20 minutes. Then, after cooling to room temperature, ultraviolet rays of 400 mJ / cm ² were irradiated through a negative mask. Then, the unexposed portion of the resin was removed with a 1.5% aqueous sodium carbonate solution (30 ° C.) for 100 seconds. Further, heat curing was performed at 140 ° C. for 60 minutes to obtain a printed wiring board on which a solder register pattern was formed.

When this substrate was immersed in methylene chloride and methyl ethyl ketone, it was found that the resin swelled and peeled off from the circuit, resulting in poor solvent resistance.

Comparative Example 2 Copolymer A of Example 1 100 parts Trimethylolpropane triacrylate 40 Cresol novolac type epoxy resin 30 (YDCN-701 manufactured by Toto Kasei Kogyo Co., Ltd.) 3 parts diethylthioxanthone (DETX manufactured by Nippon Kayaku Co., Ltd.) 2,2 -Dimethoxy-2-phenylacetophenone 4 (Irgacure-651 manufactured by Ciba Geigy) Aerosil @ 300 (manufactured by Nippon Aerosil) 6 2-phenyl-4,5-dihydroxymethylimidazole 3 (2PHZ manufactured by Shikoku Chemicals) Silicone-based defoaming Agent 2 (KS-603 manufactured by Shin-Etsu Silicone Co., Ltd.) was taken and sufficiently kneaded with a three-roll mill to obtain a uniform resin composition. This was coated on a printed wiring board on which circuits were previously wired through a 150-mesh Tetron screen. After drying at 80 ° C for 20 minutes and cooling to room temperature, 500m through a negative mask
Irradiated with ultraviolet rays of J / cm ² and then tried to remove the unexposed part of the resin with a 1.5% aqueous sodium carbonate solution (30 ° C.)
The exposed portion was whitened and expanded, and a desired printed wiring board could not be obtained.

〔The invention's effect〕

In the production of printed wiring boards, the heat-resistant photosensitive resin composition of the present invention has excellent heat resistance, adhesion, and chemical resistance as solder resists, etching resists, and plating resists. Obtainable.

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula: (Where X is a hydrogen atom or a methyl group, and Y is a carbon atom 1
, An alkylene group having 1 to 4 carbon atoms, Z is an alkyl group having 1 to 4 carbon atoms or a benzyl group), and 10 to 30% by weight of an ethylenically unsaturated compound having a carboxyl group and 10 to 30% by weight. A polymer b, an epoxidized triazine c, a photopolymerizable monomer d, a photopolymerization initiator e, and a solid powder obtained by blending 40 to 80% by weight of a polymerizable ethylenically unsaturated compound and copolymerizing the same. A heat-resistant photosensitive resin composition as an essential component.